Herbicidal compositions containing glyphosate

ABSTRACT

The invention relates to biocide compositions, comprising (a) at least one dialkylamide based on oleic and/or linoleic acid, and (b) at least one biocide. The compositions exhibit an improved stability even if stored at temperatures between 5° and 40° C. for an extended period.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is the National Phase entry of PCT/EP2008/001115, filedFeb. 14, 2008 which claims priority to EPO patent application number07003722 filed Feb. 23, 2007 both of which are incorporated herein byreference in their entireties.

FIELD OF THE INVENTION

The present invention relates to the area of agrochemicals and refers tobiocide compositions comprising certain dialkylamides, and to the use ofsuch dialkylamides as solvents or dispersants for biocides.

BACKGROUND OF THE INVENTION

Biocides, and in particular pesticides such as fungicides, insecticidesand herbicides, are important auxiliary agents for agriculture in orderto protect and to increase the yield of crops. Depending on the variousand often very specific needs, a number of actives exist, which showvery different chemical structures and behaviours. Nevertheless, it iswell known from the state of the art that it remains difficult toprepare aqueous solutions of these actives exhibiting a satisfactorystability, especially if stored over a longer time at very low orelevated temperatures. As a matter of fact, the solutions show a strongtendency to either separate or form crystals, which makes it necessaryto re-disperse the actives in the compositions prior to everyapplication in order to obtain a homogenous product. Due to the factthat in spray equipments, which is customarily used for the applicationof aqueous formulations of plant treatment agents, several filters andnozzles are present, an additional problem appears which is related tothe blocking of these filters and nozzles as a result of crystallizingactive compound during the application of aqueous spray liquors based onsolid active ingredients.

European patent application EP 0453899 B1 (Bayer) discloses the use ofdimethylamides derived from saturated C₆-C₂₀ fatty acids ascrystallisation inhibitors for azol derivatives which can be applied asfungicides. Unfortunately, the dimethylamides suggested in the patentare useful for a limited number of actives. Even in case of azols andazol derivatives the ability to inhibit unwanted crystallisation islimited to ambient temperatures, while the products are close to beinguseless in case the solutions have to be used at temperatures of about 5to 10° C.

Therefore the problem underlying the present invention has been to avoidthe disadvantages of the state of the art and develop new compositionswith improved storage stability and reduced tendency to form crystalsfor a wide range of biocides within a temperature range between 5 and40° C.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention refers to biocide compositions, comprising

-   -   (a) at least one dialkylamide based on oleic or linoleic acid,        and    -   (b) at least one biocide.

Surprisingly it has been observed that dialkylamides, and preferablydimethylamides obtained from oleic acid or linoleic acid, in particulardimethylamide obtained from colza, soy, sunflower or rape seed acid,show an improved solubilising power compared to dimethylamides fromfatty acids as known from the state of the art. Applicant has found thatthe unsaturated dialkylamides are able to dissolve or disperse a widerange of biocides even under drastic conditions, which means storagetimes of at least 4 weeks at temperatures between 5 and 40° C. withoutphase separation or sedimentation.

Dialkylamides

Dialkylamides according to the present invention (component a) can bederived from oleic acid/and or linoleic acid, and more particularly fromtechnical fatty acids rich in said species. Preferably the dialkylamidesfollow the general formula (I),R¹CO—NR²R³  (I)in which R¹CO stands for a radical of oleic acid or linoleic acid, andR² and R³ independently represent hydrogen or alkyl groups having 1 to 4carbon atoms. The preferred dialkylamides represent dimethylamides. Themost preferred species exhibiting the best performance in dissolving ordispersing a wide number of different biocides over a long period andboth at low and high temperatures is a mixture of oleic and linoleicacid dimethylamide, preferably in weight ratios of about 10:90 to about90:10, more preferably about 25:75 to about 75:25, and most preferablyabout 40:60 to 60:40, as obtained from technical grade colza, rape seed,soy or sunflower fatty acids.Biocides

A biocide (component b) is a chemical substance capable of killingdifferent forms of living organisms used in fields such as medicine,agriculture, forestry, and mosquito control. Usually, biocides aredivided into two sub-groups:

-   -   pesticides, which includes fungicides, herbicides, insecticides,        algicides, moluscicides, miticides and rodenticides, and    -   antimicrobials, which includes germicides, antibiotics,        antibacterials, antivirals, antifungals, antiprotozoals and        antiparasites.

Biocides can also be added to other materials (typically liquids) toprotect the material from biological infestation and growth. Forexample, certain types of quaternary ammonium compounds (quats) can beadded to pool water or industrial water systems to act as an algicide,protecting the water from infestation and growth of algae.

Pesticides

The U.S. Environmental Protection Agency (EPA) defines a pesticide as“any substance or mixture of substances intended for preventing,destroying, repelling, or mitigating any pest”.^([1]) A pesticide may bea chemical substance or biological agent (such as a virus or bacteria)used against pests including insects, plant pathogens, weeds, mollusks,birds, mammals, fish, nematodes (roundworms) and microbes that competewith humans for food, destroy property, spread disease or are anuisance. In the following examples, pesticides suitable for theagrochemical compositions according to the present invention are given:

Fungicides

-   -   A fungicide is one of three main methods of pest        control-chemical control of fungi in this case. Fungicides are        chemical compounds used to prevent the spread of fungi in        gardens and crops. Fungicides are also used to fight fungal        infections. Fungicides can either be contact or systemic. A        contact fungicide kills fungi when sprayed on its surface. A        systemic fungicide has to be absorbed by the fungus before the        fungus dies. Examples for suitable fungicides, according to the        present invention, encompass the following species:        (3-ethoxypropyl)mercury bromide, 2-methoxyethylmercury chloride,        2-phenylphenol, 8-hydroxyquinoline sulfate,        8-phenylmercurioxyquinoline, acibenzolar, acylamino acid        fungicides, acypetacs, aldimorph, aliphatic nitrogen fungicides,        allyl alcohol, amide fungicides, ampropylfos, anilazine, anilide        fungicides, antibiotic fungicides, aromatic fungicides,        aureofungin, azaconazole, azithirami, azoxystrobin, barium        polysulfide, to benalaxyl, benalaxyl-M, benodanil, benomyl,        benquinox, bentaluron, benthiavalicarb, benzalkonium chloride,        benzamacril, benzamide fungicides, benzamorf, benzanilide        fungicides, benzimidazole fungicides, benzimidazole precursor        fungicides, benzimidazolylcarbamate fungicides, benzohydroxamic        acid, benzothiazole fungicides, bethoxazin, binapacryl,        biphenyl, bitertanol, bithionol, blasticidin-S, Bordeaux        mixture, boscalid, bridged diphenyl fungicides, bromuconazole,        bupirimate, Burgundy mixture, buthiobate, butylamine, calcium        polysulfide, captafol, captan, carbamate fungicides, carbamorph,        carbanilate fungicides, carbendazim, carboxin, carpropamid,        carvone, Cheshunt mixture, chinomethionat, chlobenthiazone,        chloraniformethan, chloranil, chlorfenazole,        chlorodinitronaphthalene, chloroneb, chloropicrin,        chlorothalonil, chlorquinox, chlozolinate, ciclopirox,        climbazole, clotrimazole, conazole fungicides, conazole        fungicides (imidazoles), conazole fungicides (triazoles),        copper(II) acetate, copper(II) carbonate, basic, copper        fungicides, copper hydroxide, copper naphthenate, copper oleate,        copper oxychloride, copper(II) sulfate, copper sulfate, basic,        copper zinc chromate, cresol, cufraneb, cuprobam, cuprous oxide,        cyazofamid, cyclafuramid, cyclic dithiocarbamate fungicides,        cycloheximide, cyflufenamid, cymoxanil, cypendazole,        cyproconazole, cyprodinil, dazomet, DBCP, debacarb, decafentin,        dehydroacetic acid, dicarboximide fungicides, dichlofluanid,        dichlone, dichlorophen, dichlorophenyl, dicarboximide        fungicides, dichlozoline, diclobutrazol, diclocymet,        diclomezine, dicloran, diethofencarb, diethyl pyrocarbonate,        difenoconazole, diflumetorim, dimethirimol, dimethomorph,        dimoxystrobin, diniconazole, dinitrophenol fungicides,        dinobuton, dinocap, dinocton, dinopenton, dinosulfon,        dinoterbon, diphenylamine, dipyrithione, disulfuram, ditalimfos,        dithianon, dithiocarbamate fungicides, DNOC, dodemorph, dodicin,        dodine, DONATODINE, drazoxolon, edifenphos, epoxiconazole,        etaconazole, etem, ethaboxam, ethirimol, ethoxyquin,        ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury        acetate, ethylmercury bromide, ethylmercury chloride,        ethylmercury phosphate, etridiazole, famoxadone, fenamidone,        fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram,        fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin,        fenpropimorph, fentin, ferbam, ferimzone, fluazinam,        fludioxonil, flumetover, flumorph, fluopicolide, fluoroimide,        fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole,        flusulfamide, flutolanil, flutriafol, folpet, formaldehyde,        fosetyl, fuberidazole, furalaxyl, furametpyr, furamide        fungicides, furanilide fungicides, furcarbanil, furconazole,        furconazole-cis, furfural, furmecyclox, furophanate, glyodin,        griseofulvin, guazatine, halacrinate, hexachlorobenzene,        hexachlorobutadiene, hexachlorophene, hexaconazole,        hexylthiofos, hydrargaphen, hymexazol, imazalil, imibenconazole,        imidazole fungicides, iminoctadine, inorganic fungicides,        inorganic mercury fungicides, iodomethane, ipconazole,        iprobenfos, iprodione, iprovalicarb, isoprothiolane,        isovaledione, kasugamycin, kresoxim-methyl, lime sulphur,        mancopper, mancozeb, maneb, mebenil, mecarbinzid, mepanipyrim,        mepronil, mercuric chloride, mercuric oxide, mercurous chloride,        mercury fungicides, metalaxyl, metalaxyl-M, metam, metazoxolon,        metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl        isothiocyanate, methylmercury benzoate, methylmercury        dicyandiamide, methylmercury pentachlorophenoxide, metiram,        metominostrobin, metrafenone, metsulfovax, milneb, morpholine        fungicides, myclobutanil, myclozolin,        N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin,        nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone,        ofurace, organomercury fungicides, organophosphorus fungicides,        organotin fungicides, orysastrobin, oxadixyl, oxathiin        fungicides, oxazole fungicides, oxine copper, oxpoconazole,        oxycarboxin, pefurazoate, pe nconazole, penc ycuron, pe        ntachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercury        acetate, phenylmercury chloride, phenylmercury derivative of        pyrocatechol, phenylmercury nitrate, phenylmercury salicylate,        phenylsulfamide fungicides, phosdiphen, phthalide, phthalimide        fungicides, picoxystrobin, piperalin, polycarbamate, polymeric        dithiocarbamate fungicides, polyoxins, polyoxorim, polysulfide        fungicides, potassium azide, potassium polysulfide, potassium        thiocyanate, probenazole, prochloraz, procymidone, propamocarb,        propiconazole, propineb, proquinazid, prothiocarb,        prothioconazole, pyracarbolid, pyraclostrobin, pyrazole        fungicides, pyrazophos, pyridine fungicides, pyridinitril,        pyrifenox, pyrimethanil, pyrimidine fungicides, pyroquilon,        pyroxychlor, pyroxyfur, pyrrole fungicides, quinacetol,        quinazamid, quinconazole, quinoline fungicides, quinone        fungicides, quinoxaline fungicides, quinoxyfen, quintozene,        rabenzazole, salicylanilide, silthiofam, simeconazole, sodium        azide, sodium orthophenylphenoxide, sodium pentachlorophenoxide,        sodium polysulfide, spiroxamine, streptomycin, strobilurin        fungicides, sulfonanilide fungicides, sulfur, sultropen, TCMTB,        tebuconazole, tecloftalam, tecnazene, tecoram, tetraconazole,        thiabendazole, thiadifluor, thiazole fungicides, thicyofen,        thifluzamide, thiocarbamate fungicides, thiochlorfenphim,        thiomersal, thiophanate, thiophanate-methyl, thiophene        fungicides, thioquinox, thiram, tiadinil, tioxymid, tivedo,        tolclofos-methyl, tolnaftate, tolylfluanid, tolylmercury        acetate, triadimefon, triadimenol, triamiphos, triarimol,        triazbutil, triazine fungicides, triazole fungicides,        triazoxide, tributyltin oxide, trichlamide, tricyclazole,        tridemorph, trifloxystrobin, triflumizole, triforine,        triticonazole, unclassified fungicides, undecylenic acid,        uniconazole, urea fungicides, validamycin, valinamide        fungicides, vinclozolin, zarilamid, zinc naphthenate, zineb,        ziram, zoxamide and their mixtures.

Herbicides

-   -   An herbicide is a pesticide used to kill unwanted plants.        Selective herbicides kill specific targets while leaving the        desired crop relatively unharmed. Some of these act by        interfering with the growth of the weed and are often based on        plant hormones. Herbicides used to clear waste ground are        nonselective and kill all plant material with which they come        into contact. Herbicides are widely used in agriculture and in        landscape turf management. They are applied in total vegetation        control (TVC) programs for maintenance of highways and        railroads. Smaller quantities are used in forestry, pasture        systems, and management of areas set aside as wildlife habitat.        In the following, a number of suitable herbicides are compiled:        -   2,4-D, a broadleaf herbicide in the phenoxy group used in            turf and in no-till field crop production. Now mainly used            in a blend with other herbicides that act as synergists, it            is the most widely used herbicide in the world, the third            most commonly used in the United States. It is an example of            synthetic auxin (plant hormone).        -   Atrazine, a triazine herbicide used in corn and sorghum for            control of broadleaf weeds and grasses. It is still used            because of its low cost and because it works as a synergist            when used with other herbicides, it is a photosystem II            inhibitor.        -   Clopyralid, a broadleaf herbicide in the pyridine group,            used mainly in turf, rangeland, and for control of noxious            thistles. Notorious for its ability to persist in compost.            It is another example of synthetic auxin.        -   Dicamba, a persistent broadleaf herbicide active in the            soil, used on turf and field corn. It is another example of            synthetic auxin.        -   Glyphosate, a systemic nonselective (it kills any type of            plant) herbicide used in no-till burndown and for weed            control in crops that are genetically modified to resist its            effects. It is an example of a EPSPs inhibitor.        -   Imazapyr, a non-selective herbicide used for the control of            a broad range of weeds including terrestrial annual and            perennial grasses and broadleaved herbs, woody species, and            riparian and emergent aquatic species.        -   Imazapic, a selective herbicide for both the pre- and            post-emergent control of some annual and perennial grasses            and some broadleaf weeds. Imazapic kills plants by            inhibiting the production of branched chain amino acids            (valine, leucine, and isoleucine), which are necessary for            protein synthesis and cell growth.        -   Metoalachlor, a pre-emergent herbicide widely used for            control of annual grasses in corn and sorghum; it has            largely replaced atrazine for these uses.        -   Paraquat, a nonselective contact herbicide used for no-till            burndown and in aerial destruction of marijuana and coca            plantings. It is more acutely toxic to people than any other            herbicide in widespread commercial use.        -   Picloram, a pyridine herbicide mainly used to control            unwanted trees in pastures and edges of fields. It is            another synthetic auxin.        -   Triclopyr.

Insecticides

-   -   An insecticide is a pesticide used against insects in all        developmental forms. They include ovicides and larvicides used        against the eggs and larvae of insects. Insecticides are used in        agriculture, medicine, industry and the household. In the        following, suitable insecticides are mentioned:        -   Chlorinated insecticides such as, for example, Camphechlor,            DDT, Hexachlorocyclohexane, gamma-Hexachlorocyclohexane,            Methoxychlor, Pentachlorophenol, TDE, Aldrin, Chlordane,            Chlordecone, Dieldrin, Endosulfan, Endrin, Heptachlor, Mirex            and their mixtures;        -   Organophosphorus compounds such as, for example, Acephate,            Azinphos-methyl, Bensulide, Chlorethoxyfos, Chlorpyrifos,            Chlorpyriphos-methyl, Diazinon, Dichlorvos (DDVP),            Dicrotophos, Dimethoate, Disulfoton, Ethoprop, Fenamiphos,            Fenitrothion, Fenthion, Fosthiazate, Malathion,            Methamidophos, Methidathion, Methyl-parathion, Mevinphos,            Naled, Omethoate, Oxydemeton-methyl, Parathion, Phorate,            Phosalone, Phosmet, Phostebupirim, Pirimiphos-methyl,            Profenofos, Terbufos, Tetrachlorvinphos, Tribufos,            Trichlorfon and their mixtures;        -   Carbamates such as, for example, Aldicarb, Carbofuran,            Carbaryl, Methomyl, 2-(1-Methylpropyl)phenyl methylcarbamate            and their mixtures;        -   Pyrethroids such as, for example, Allethrin, Bifenthrin,            Deltamethrin, Permethrin, Resmethrin, Sumithrin,            Tetramethrin, Tralomethrin, Transfluthrin and their            mixtures;        -   Plant toxin derived compounds such as, for example, Derris            (rotenone), Pyrethrum, Neem (Azadirachtin), Nicotine,            Caffeine and their mixtures.

Rodenticides

-   -   Rodenticides are a category of pest control chemicals intended        to kill rodents. Rodents are difficult to kill with poisons        because their feeding habits reflect their place as scavengers.        They would eat a small bit and wait, and if they do not get        sick, they would continue eating. An effective rodenticide must        be tasteless and odorless in lethal concentrations, and have a        delayed effect. In the following, examples for suitable        rodenticides are given:        -   Anticoagulants are defined as chronic (death occurs after            1-2 weeks after ingestion of the lethal dose, rarely            sooner), single-dose (second generation) or multiple dose            (first generation) cumulative rodenticides. Fatal internal            bleeding is caused by a lethal dose of anticoagulants such            as brodifacoum, coumatetralyl or warfarin. These substances            in effective doses are antivitamins K, blocking the enzymes            K₁-2,3-epoxide-reductase (this enzyme is preferentially            blocked by 4-hydroxycoumarin/4-hydroxythiacoumarin            derivatives) and K₁-quinone-reductase (this enzyme is            preferentially blocked by indandione derivatives), depriving            the organism of its source of active vitamin K₁. This leads            to a disruption of the vitamin K cycle, resulting in an            inability of production of essential blood-clotting factors            (mainly coagulation factors II (prothrombin), VII            (proconvertin), IX (Christmas factor) and X (Stuart            factor)). In addition to this specific metabolic disruption,            toxic doses of 4-hydroxycoumarin/4-hydroxythiacoumarin and            indandione anticoagulants are causing damage to tiny blood            vessels (capillaries), increasing their permeability,            causing diffuse internal bleedings (haemorrhagias). These            effects are gradual; they develop in the course of days and            are not accompanied by any nociceptive perceptions such as            pain or agony. In the final phase of the intoxication, the            exhausted rodent collapses in hypovolemic circulatory shock            or severe anemia and dies calmly. Rodenticidal            anticoagulants are either first generation agents            (4-hydroxycoumarin type: warfarin, coumatetralyl; indandione            type: pindone, diphacinone, chlorophacinone), generally            requiring higher concentrations (usually between 0.005 and            0.1%), a consecutive intake over days in order to accumulate            the lethal dose, they are not very active or inactive after            a single feeding and less toxic than second generation            agents, which are derivatives of 4-hydroxycoumarin            (difenacoum, brodifacoum, bromadiolone and flocoumafen) or            4-hydroxy-1-benzothiin-2-one (4-hydroxy-1-thiacoumarin,            sometimes incorrectly referred to as            4-hydroxy-1-thiocoumarin, for reason see heterocyclic            compounds), namely difethialone. Second generation agents            are far more toxic than first generation agents. They are            generally applied in lower concentrations in baits (usually            in the order of 0.001-0.005%), and are lethal after single            ingestion of bait and are effective also against strains of            rodents that have become resistant against first generation            anticoagulants; thus the second to generation anticoagulants            are sometimes referred to as “superwarfarins”. Sometimes            anticoagulant rodenticides are potentiated by an antibiotic,            most commonly the sulfaquinoxaline. The aim of this            association (e.g. warfarin 0.05%+sulfaquinoxaline 0.02%, or            difenacoum 0.005%+sulfaquinoxaline 0.02% etc.) is that the            antibiotic/bacteriostatic agent suppresses intestinal/gut            symbiotic microflora that represents a source of vitamin K.            Thus the symbiotic bacteriae are killed, or their metabolism            is impaired and the production of vitamin K by them is            diminuted, an effect which logically contributes to the            action of anticoagulants. Antibiotic agents other than            sulfaquinoxaline may be used, for example co-trimoxazole,            tetracycline, neomycin or metronidazole. A further synergism            used in rodenticidal baits is that of an association of an            anticoagulant with a compound with vitamin D-activity, i.e.            cholecalciferol or ergocalciferol, (see below). A typical            formula used is, e.g., warfarin 0.025-0.05%+cholecalciferol            0.01%. In some countries there are even fixed            three-component rodenticides, i.e.            anticoagulant+antibiotic+vitamin D, e.g. difenacoum            0.005%+sulfaquinoxaline 0.02%+cholecalciferol 0.01%.            Associations of a second-generation anticoagulant with an            antibiotic and/or vitamin D are considered to be effective            even against the most resistant strains of rodents, though            some second generation anticoagulants (namely brodifacoum            and difethialone), in bait concentrations of 0.0025-0.005%            are so toxic that no known resistant strain of rodents            exists, and even rodents resistant against any other            derivatives are reliably exterminated by application of            these most toxic anticoagulants.        -   Vitamin K₁ has been suggested, and successfully used, as an            antidote for pets or humans who and which were either            accidentally or intentionally (poison assaults on pets,            suicidal attempts) exposed to anticoagulant poisons. In            addition, since some of these poisons act by inhibiting            liver functions, and in progressed stages of poisoning,            several blood-clotting factors as well as the whole volume            of circulating blood are missing. A blood transfusion            (optionally with the clotting factors present) can save a            person's life, who inadvertently took them, which is an            advantage over some older poisons.        -   Metal phosphides have been used as a means of killing            rodents and are considered single-dose fast acting            rodenticides (death occurs commonly within 1-3 days after            single bait ingestion). A dose of bait consisting of food            and a phosphide (usually zinc phosphide) is left where the            rodents can eat it. The acid in the digestive system of the            rodent reacts with the phosphide to generate the toxic            phosphine gas. This method of vermin control has possible            use in places where rodents are resistant to some of the            anticoagulants, particularly for control of house and field            mice; zinc phosphide baits are also cheaper than most            second-generation anticoagulants, so that sometimes, in            cases of large infestation by rodents, their population is            initially reduced by copious amounts of zinc phosphide bait            applied, and the rest of the population that survived the            initial fast-acting poison is then eradicated by prolonged            feeding on anticoagulant bait. Inversely, the individual            rodents that survived anticoagulant bait poisoning (rest            population) can be eradicated by pre-baiting them with            nontoxic bait for a week or two (this is important in order            to overcome bait shyness and to get rodents used to feeding            in specific areas by offering specific food, especially when            eradicating rats) and subsequently applying poisoned bait of            the same sort as used for pre-baiting until all consumption            of the bait ceases (usually within 2-4 days). These methods            of alternating rodenticides with different modes of action            provides a factual or an almost 100% eradication of the            rodent population in the area if the acceptance/palatability            of bait is good (i.e., rodents readily feed on it).        -   Phosphides are rather fast acting rat poisons, resulting in            that the rats are dying usually in open areas instead of the            affected buildings. Typical examples are aluminum phosphide            (fumigant only), calcium phosphide (fumigant only),            magnesium phosphide (fumigant only) and zinc phosphide (in            baits). Zinc phosphide is typically added to rodent baits in            amounts of around 0.75-2%. The baits have a strong, pungent            garlic-like odor characteristic for phosphine liberated by            hydrolysis. The odor attracts (or, at least, does not            repulse) rodents, but it has a repulsive effect on other            mammals; birds, however (notably wild turkeys), are not            sensitive to the smell. They feed on the bait thus becoming            collateral damage.        -   Hypercalcemia. Calciferols (vitamins D), cholecalciferol            (vitamin D₃) and ergocalciferol (vitamin D₂) are used as            rodenticides, which are toxic to rodents for the same reason            that they are beneficial to mammals: they are affecting            calcium and phosphate homeostasis in the body. Vitamins D            are essential in minute quantities (few IUs per kilogram            body weight daily, which is only a fraction of a milligram),            and like most fat soluble vitamins, they are toxic in larger            doses as they readily result in the so-called            hypervitaminosis, which is, simply said, poisoning by the            vitamin. If the poisoning is severe enough (that is if the            dose of the toxicant is high enough), it eventually leads to            death. In rodents consuming the rodenticidal bait it causes            hypercalcemia by raising the calcium level, mainly by            increasing calcium absorption from food, mobilising            bone-matrix-fixed calcium into ionised form (mainly            monohydrogencarbonate calcium cation, partially bound to            plasma proteins, [CaHCO₃]⁺), which circulates dissolved in            the blood plasma, and after ingestion of a lethal dose the            free calcium levels are raised sufficiently so that blood            vessels, kidneys, the stomach wall and lungs are            mineralised/calcificated (formation of calcificates,            crystals of calcium salts/complexes in the tissues, thus            damaging them), further leading to heart problems (myocard            is sensitive to variations of free calcium levels which are            affecting both myocardial contractibility and excitation            propagation between atrias and ventriculas) and bleeding            (due to capillary damage), and possibly kidney failure. It            is considered to be single-dose, or cumulative (depending on            the concentration used; the common 0.075% bait concentration            is lethal to most rodents after a single intake of larger            portions of the bait), sub-chronic (death occurring usually            within days to one week after ingestion of the bait).            Applied concentrations are 0.075% cholecalciferol and 0.1%            ergocalciferol when used alone. There is an important            feature of calciferols toxicology which is that they are            synergistic with anticoagulant toxicants. This means that            mixtures of anticoagulants and calciferols in the same bait            are more toxic than the sum of toxicities of the            anticoagulant and the calciferol in the bait, so that a            massive hypercalcemic effect can be achieved by a            substantially lower calciferol content in the bait and            vice-versa. More pronounced anticoagulant/hemorrhagic            effects are observed if calciferol is present. This            synergism is mostly used in baits low in calciferol because            effective concentrations of calciferols are more expensive            than effective concentrations of the most anticoagulants.            The historically very first application of a calciferol in            rodenticidal bait was, in fact, the Sorex product Sorexa® D            (with a different formula than today's Sorexa® D) back in            the early 1970's, containing warfarin 0.025%+ergocalciferol            0.1%. Today, Sorexa® CD contains a 0.0025% difenacoum+0.075%            cholecalciferol combination. Numerous other brand products            containing either calciferols 0.075-0.1% (e.g. Quintox®,            containing 0.075% cholecalciferol) alone, or a combination            of calciferol 0.01-0.075% with an anticoagulant are            marketed.    -   Miticides, Moluscicides and Nematicides        -   Miticides are pesticides that kill mites. Antibiotic            miticides, carbamate miticides, formamidine miticides, mite            growth regulators, organochlorine, permethrin and            organophosphate miticides all belong to this category.        -   Molluscicides are pesticides used to control mollusks, such            as moths, slugs and snails. These substances include            metaldehyde, methiocarb and aluminium sulfate. A nematicide            is a type of chemical pesticide used to kill parasitic            nematodes (a phylum of worm).        -   A nematicide is obtained from a neem tree's seed cake; which            is the residue of neem seeds after oil extraction. The neem            tree is known by several names in the world but was first            cultivated in India since ancient times.

Antimicrobials

In the following examples, antimicrobials suitable for agrochemicalcompositions according to the present invention are given. Bactericidaldisinfectants mostly used are those applying

-   -   active chlorine (i.e., hypochlorites, chloramines,        dichloroisocyanurate and trichloroisocyanurate, wet chlorine,        chlorine dioxide, etc.),    -   active oxygen (peroxides such as peracetic acid, potassium        persulfate, sodium perborate, sodium percarbonate and urea        perhydrate),    -   iodine (iodpovidone (povidone-iodine, Betadine), Lugol's        solution, iodine tincture, iodinated nonionic surfactants),    -   concentrated alcohols (mainly ethanol, 1-propanol, called also        n-propanol and 2-propanol, called isopropanol and mixtures        thereof; further, 2-phenoxyethanol and 1- and 2-phenoxypropanols        are used),    -   phenolic substances (such as phenol (also called “carbolic        acid”), cresols (called “Lysole” in combination with liquid        potassium soaps), halogenated (chlorinated, brominated) phenols,        such as hexachlorophene, triclosan, trichlorophenol,        tribromophenol, pentachlorophenol, Dibromol and salts thereof),    -   cationic surfactants such as some quaternary ammonium cations        (such as benzalkonium chloride, cetyl trimethylammonium bromide        or chloride, didecyldimethylammonium chloride, cetylpyridinium        chloride, benzethonium chloride) and others, non-quarternary        compounds such as chlorhexidine, glucoprotamine, octenidine        dihydrochloride, etc.),    -   strong oxidizers such as ozone and permanganate solutions;    -   heavy metals and their salts such as colloidal silver, silver        nitrate, mercury chloride, phenylmercury salts, copper sulfate,        copper oxide-chloride etc. Heavy metals and their salts are the        most toxic and environmentally hazardous bactericides and,        therefore, their use is strongly suppressed or forbidden.    -   Further, also    -   properly concentrated strong acids (phosphoric, nitric,        sulfuric, amidosulfuric, toluenesulfonic acids) and    -   alkalis (sodium, potassium, calcium hydroxides),    -   at pH <1 or >13, respectively, particularly below at elevated        temperatures (above 60° C.) kill bacteria.    -   As antiseptics (i.e., germicide agents that can be used on human        or animal body, skin, mucoses, wounds and the like), few of the        above mentioned disinfectants can be used under proper        conditions (mainly concentration, pH, temperature and toxicity        toward man/animal). Among them, the following are important:        -   Some properly diluted chlorine preparations (e.g. Daquin's            solution, 0.5% sodium or potassium hypochlorite solution,            pH-adjusted to pH 7-8, or 0.5-1% solution of sodium            benzenesulfochloramide(chloramine B)), some        -   iodine preparations such as iodopovidone in various galenics            (ointment, solutions, wound plasters), in the past also            Lugol's solution,        -   peroxides as urea perhydrate solutions and pH-buffered            0.1-0.25% peracetic acid solutions,        -   alcohols with or without antiseptic additives, used mainly            for skin antisepsis,        -   weak organic acids such as sorbic acid, benzoic acid, lactic            acid and salicylic acid        -   some phenolic compounds such as hexachlorophene, triclosan            and Dibromol, and        -   cation-active compounds such as 0.05-0.5% benzalkonium,            0.5-4% chlorhexidine, 0.1-2% octenidine solutions.    -   Bactericidal antibiotics kill bacteria; bacteriostatic        antibiotics only slow down their growth or reproduction.        Penicillin is a bactericide, as are cephalosporins.        Aminoglycosidic antibiotics can act in both a bactericidal        manner (by disrupting cell wall precursor leading to lysis), or        bacteriostatic manner (by connecting to 30s ribosomal subunit        and reducing translation fidelity leading to inaccurate protein        synthesis). Other bactericidal antibiotics according to the        present invention include the fluoroquinolones, nitrofurans,        vancomycin, monobactams, co-trimoxazole, and metronidazole.        Emulsifiers

In a number of cases it is advantageous to add emulsifiers (component c)to the biocide compositions in order to support the stability of theproducts. A first preferred group of emulsifiers encompasses non-ionicsurfactants such as, for example:

-   -   products of the addition of 2 to 30 mol ethylene oxide and/or 0        to 5 mol propylene oxide onto linear C₈₋₂₂ fatty alcohols, onto        C₁₂₋₂₂ fatty acids and onto alkyl phenols containing 8 to 15        carbon atoms in the alkyl group;    -   C_(12/18) fatty acid monoesters and diesters of addition        products of 1 to 30 mol ethylene oxide onto glycerol;    -   glycerol mono- and diesters and sorbitan mono- and diesters of        saturated and unsaturated fatty acids containing 6 to 22 carbon        atoms and ethylene oxide addition products thereof;    -   addition products of 15 to 60 mol ethylene oxide onto castor oil        and/or hydrogenated castor oil;    -   polyol ester's and, in particular, polyglycerol esters such as,        for example, polyglycerol polyricinoleate, polyglycerol        poly-12-hydroxystearate or polyglycerol dimerate isostearate.        Mixtures of compounds from several of these classes are also        suitable;    -   addition products of 2 to 15 mol ethylene oxide onto castor oil        and/or hydrogenated castor oil;    -   partial esters based on linear, branched, unsaturated or        saturated C_(6/22) fatty acids, ricinoleic acid and        12-hydroxystearic acid and glycerol, polyglycerol,        pentaerythritol, dipentaerythritol, sugar alcohols (for example        sorbitol), alkyl glucosides (for example methyl glucoside, butyl        glucoside, lauryl glucoside) and polyglucosides (for example        cellulose);    -   mono-, di and trialkyl phosphates and mono-, di- and/or        tri-PEG-alkyl phosphates and salts thereof;    -   wool wax alcohols;    -   polysiloxane/polyalkyl polyether copolymers and corresponding        derivatives;    -   mixed esters of pentaerythritol, fatty acids, citric acid and        fatty alcohol and/or mixed esters of C₆₋₂₂ fatty acids, methyl        glucose and polyols, preferably glycerol or polyglycerol,    -   polyalkylene glycols and    -   glycerol carbonate.

The addition products of ethylene oxide and/or propylene oxide ontofatty alcohols, fatty acids, alkylphenols, glycerol mono- and diestersand sorbitan mono- and diesters of fatty acids to or onto castor oil areknown commercially available products. They are homologue mixtures ofwhich the average degree of alkoxylation corresponds to the ratiobetween the quantities of ethylene oxide and/or propylene oxide andsubstrate with which the addition reaction is carried out. C_(12/18)fatty acid monoesters and diesters of addition products of ethyleneoxide onto glycerol are known as lipid layer enhancers for cosmeticformulations. The preferred emulsifiers are described in more detail asfollows:

Partial Glycerides

Typical examples of suitable partial glycerides are hydroxystearic acidmonoglyceride, hydroxystearic acid diglyceride, isostearic acidmonoglyceride, isostearic acid diglyceride, oleic acid monoglyceride,oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic aciddiglyceride, linoleic acid monoglyceride, linoleic acid diglyceride,linolenic acid monoglyceride, linolenic acid diglyceride, erucic acidmonoglyceride, erucic acid diglyceride, tartaric acid monoglyceride,tartaric acid diglyceride, citric acid monoglyceride, citric aciddiglyceride, malic acid monoglyceride, malic acid diglyceride andtechnical mixtures thereof which may still contain small quantities oftriglyceride from the production process. Addition products of 1 to 30,and preferably 5 to 10, mol ethylene oxide onto the partial glyceridesmentioned are also suitable.

Sorbitan Esters

Suitable sorbitan esters are sorbitan monoisostearate, sorbitansesquiisostearate, sorbitan diisostearate, sorbitan triisostearate,sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitantrioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitandierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitansesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate,sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitandihydroxystearate, sorbitan tri hydroxystearate, sorbitan monotartrate,sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tri tartrate,sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate,sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate,sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof.Addition products of 1 to 30, and preferably 5 to 10, mol ethylene oxideonto the sorbitan esters mentioned are also suitable.

Polyglycerol Esters

Typical examples of suitable polyglycerol esters are Polyglyceryl-2Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate(Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® GI 34),Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate(Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450),Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate(Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane®NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and PolyglycerylPolyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate andmixtures thereof. Examples of other suitable polyolesters are the mono-,di- and triesters of trimethylol propane or pentaerythritol with lauricacid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid,oleic acid, behenic acid and the like, optionally reacted with 1 to 30mol ethylene oxide.

Typical anionic emulsifiers are aliphatic C₁₂₋₂₂ fatty acids such aspalmitic acid, stearic acid or behenic acid, for example, and C₁₂₋₂₂dicarboxylic acids such as azelaic acid or sebacic acid, for example.

Other suitable emulsifiers are zwitterionic surfactants. Zwitterionicsurfactants are surface-active compounds which contain at least onequaternary ammonium group and at least one carboxylate and one sulfonategroup in the molecule. Particularly suitable zwitterionic surfactantsare the so-called betaines such as the N-alkyl-N,N-dimethyl ammoniumglycinates, for example cocoalkyl dimethyl ammonium glycinate,N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for examplecocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethyl carboxymethyl glycinate. The fatty acid amide derivativeknown under the CTFA name of Cocamidopropyl Betaine is particularlypreferred. Ampholytic surfactants are also suitable emulsifiers.Ampholytic surfactants are surface-active compounds which, in additionto a C_(8/18) alkyl or acyl group, contain at least one free amino groupand at least one —COOH— or —SO₃H— group in the molecule and which arecapable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkyl-aminopropionic acids and alkylaminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-cocoalkylaminopropionate,cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine.

Biocide Compositions

Typically, the compositions according to the present invention comprise

-   (a) about 0.1% b.w. to about 99% b.w., preferably about 5% b.w. to    about 90% b.w., and most preferably about 15% b.w. to about 25%    b.w., dialkylamides derived from oleic acid and/or linoleic acid,-   (b) about 1% b.w. to about 99.1% b.w., preferably about 2% b.w. to    about 80% b.w., and most preferably about 5% b.w. to about 15% b.w.,    biocides, and-   (c) 0 b.w. to about 10% b.w., and preferably 1 to 5% b.w.,    emulsifiers    on condition that the amounts add with water to 100% b.w. Usually,    the active matter content (which means the sum of components a+b+c)    is about 5% b.w. to about 50% b.w., and preferably about 10% b.w. to    about 25% b.w., calculated on the total of the aqueous composition.

INDUSTRIAL APPLICATION

A final embodiment of the present invention is related to the use ofdialkylamides based on oleic acid and/or linoleic acid, in particulardimethylamides based on technical grade colza, rape seed, soy orsunflower acid as solvents or dispersants for biocides.

EXAMPLES Examples 1 to 6, Comparative Examples C1 and C2

Several aqueous concentrates were prepared by mixing biocides,dimethylamides and emulsifiers in water until a homogeneous solution wasobtained. The concentrates were subsequently diluted with water in orderto achieve an active matter concentration of 10% b.w. The products thusobtained were stored over a period of 10 to 40 days at temperatures of5, 20 and 40° C. The stability of the mixtures was observed byinspection and determined according to the following scale: (++)=stable;(+)=slight phase separation/formation of some crystals; (o)=significantphase separation/sedimentation; (−) phases clearly separated/strongsedimentation of crystals. The results are compiled in Table 1. Theamounts reflect the composition of the concentrates.

TABLE 1 Stability of biocide compositions 1 2 3 4 5 6 C1 C2 Composition[% b.w.] Biphenyl 35 — — — — — — — Glyphosphate — — — — 25 — 35 —Deltametrin — — 35 — — 25 — 35 Glucoprotamin — — — 35 — — — — Lacticacid dimethylamide 25 25 25 25 15 15 — — Stearic acid dimethylamide — —— — — — 25 25 Sorbitanmono/dilaurate + 20EO 10 10  5  5 — — — —Polyglyceryl-2 — —  5  5 10 10 — — Dipolyhydroxystearate Water add to100 Stability after 10 days, 5° C. ++ ++ ++ ++ ++ ++ ∘ ∘ after 20 days,5° C. + + ++ ++ ++ ++ − − after 40 days, 5° C. ∘ ∘ + + + ++ − − after 10days, 20° C. ++ ++ ++ ++ ++ ++ ++ ++ after 20 days, 20° C. ++ ++ ++ ++++ ++ ++ ++ after 40 days, 20° C. ++ ++ ++ ++ ++ ++ + + after 10 days,40° C. ++ ++ ++ ++ ++ ++ + + after 20 days, 40° C. ++ ++ ++ ++ ++ ++ ∘ ∘after 40 days, 40° C. + + + + ++ ++ ∘ ∘

What is claimed is:
 1. A herbicide composition with improved storagestability and reduced tendency to form crystals, comprising: (a) atleast one oleic acid and/or linoleic acid dialkylamide, and (b) at leastone glyphosate wherein the dialkylamide and the glyphosate are presentin a ratio effective to inhibit phase separation or sedimentation whenstored for at least 4 weeks at temperatures between 5 and 40° C.
 2. Thecomposition of claim 1 wherein component (a) comprises at least onedialkylamide of formula (I),R¹CO—NR²R³  (I) in which R¹CO represents an oleic and/or linoleic acidmoiety, and R² and R³ independently represent alkyl groups having 1 to 4carbon atoms.
 3. The composition of claim 1 wherein component (a)comprises at least one dialkylamide based on technical grade fatty acidsselected from the group consisting of colza, rape seed, soy andsunflower fatty acids.
 4. The composition of claim 1 wherein component(a) is a mixture of oleic acid dimethylamide and linoleic aciddimethylamide in a weight ratio of 10:90 to 90:10.
 5. The composition ofclaim 1 further comprising as component (c) at least one emulsifier. 6.A herbicide composition comprising: (a) 0.1% to 99% by weight, based onthe composition, of at least one oleic acid and/or linoleic aciddialkylamide, (b) 1% to 99.1% by weight, based on the composition, of atleast one glyphosate, and (c) 0% to 10% by weight, based on thecomposition, of at least one emulsifier provided that the amounts,including water, total 100%, and wherein the dialkylamide dissolves ordisperses the glyphosate when stored for at least 4 weeks attemperatures between 5 and 40° C. without phase separation orsedimentation.
 7. The composition of claim 6 wherein the sum ofcomponents (a)+(b)+(c) equals 5% to 50% by weight, based on thecomposition.
 8. A method of dissolving or dispersing a glyphosateherbicide comprising adding at least one oleic acid and/or linoleic aciddialkylamide to aid in dissolving or dispersing at least one glyphosatewherein the dialkylamide and the glyphosate are present in a ratioeffective to inhibit phase separation or sedimentation when stored forat least 4 weeks at temperatures between 5 and 40° C.